Acrylic diester-propionamides and polymers thereof



Patented Jan. 4, 1949 TED "STATES PA gm Price ACRYLIC DIESTER-PROPIONAMIDES AND POLYMERS THEREOF Delbert D. Reynolds and John H. Van Campen, Rochester, N. Y., assignors to Eastman Kodak Company. Rochester, N.

New J ersey,

Y., a corporation of No Drawing. Application November 22, 1947, Serial No. 787,608

6Claims. (Cl. zen-18.3) Y

The new compounds may be represented by the general structural formula:

o o o N 0112 --OOH- -NH -OQHI-OB-O=OHQ H: i in which R and R1 each represents the same or different members of the group consisting of hydrogen, a halogen atom (e. g. chlorine or bromine), a saturated alkyl group (e. g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. butyl, tert. butyl, etc.),' an aryl group (e. g. phenyl, naphthyl, tolyl, xylyl, etc.), an'aralkyl, group (e. g. benzyl, phenylethyl, etc.) an alkoxy or aryloxy group (e. g. methoxy, ethoxy, pro poxy, isopropoxy, butoxy, phenoxy, etc.), a cycloalkyl group (e. g. .cyclopropyl, cyclobutyl, cyclohexyl, etc.), an acyl group (e. g. acetyl, propionyl, butyryl, etc.), an acyloxy group (e. g. acetoxy, propionyloxy, butyryloxy, etc.), a heterocyclic group (e. g. piperidyl), a carboxyl group, a carbalkoxy group (e. g. carbmethoxy, carbethoxy, etc.) a cyano group, an amino group (e. g. dimethylamino, diphenylamino, methylphenylamino, etc.), a diacylamido group (e. g. phthalimido, etc.), and similar groups. The above-defined new diester-amides are nonresinous, crystalline or viscous liquid compounds which have distinct melting points and boiling points, and which are capable of isolation in the pure state from their preparation reaction mixtures. The monomers are soluble in most of the common organic solvents such as benzene, chloroform, dioxane, etc. They are valuable intermediates in the preparation of other useful chemical compounds. vThey are also excellent modifying agents in solution or in compositions designed for impregnating paper and textile fabrics, being capable of polymerization to insoluble resins in the particular material so lmpregnated or treated. In additlion, they are polymerizable alone or conjointly with other unsaturated compounds to shaped products which are insoluble in all the commonorganic solvents.

Such copolymers in completely polymerized state are characterized by being easily millable to the shaped object desired.

It is, accordingly, an object of the invention to provide a new class of unsaturated aliphatic diester-amides and polymers thereof. Another object is to provide a method for preparing the same. Other objects will become apparent hereinafter.

In accordance with the invention, the new diester-amides are prepared by esterlfying N-(phydroxyethyl) lactamide with acrylic anhydrlde or [Jr-substituted acrylic anhydrides, or with acrylyl chlorides having the general formula:

in an inert solvent medium such as anhydrous benzene, methyl acetate, chloroform, dioxane, etc., and in the presence of an acid-binding agent, for example, anhydrous sodium carbonate, and a dehydrating agent, for example, anhydrous calcium sulfate. This process is described and claimed in copending application, Serial No. 787,605, filed of even date herewith, in the names of Delbert D. Reynolds and William O. Kenyon. Where the acid anhydrides. are employed as the esterifying agents, the reaction can be carried out advantageously in the presence of a polymerization inhibitor such as a copper salt and in the presence of an organic base such as pyridine. The -substltuted acrylic acid chlorides, above defined, may be prepared by treating the cone sponding free acids or their esters with thionyl chloride or phosphorus chlorides. The diest'eramides may be isolated from their preparation mixtures and purified in any convenient manner, for example, as described in the examples which follow.

The polymerization of the new diester-amides of the invention alone or conjointly with one or more other unsaturated compounds is accelerated by heat, and by polymerization catalysts which are known to accelerate the polymerization of acrylic compounds. Exemplary of such catalysts are the organic peroxides (e. g.

benzoyl peroxide, acetyl peroxide and lauroyl trile, citraconoitrile, itaconoitrile, and similar compounda' The preferred copolymers of the invention are obtained with starting polymerization mixtures having from 0.2 to 99.8 parts by weight of the new monomeric diester-amide and from 99.8 to 0.2 parts by weight of one or more of the other ,.-above-mentioned unsaturated organic compounds.

merized with one or more'other ethylenic monomers having the general formulas:

wherein Y and/or Z are alkyl, aryl, aralkyl, alkoxyl, aryloxy, aralkox'yl, halogeno, acylamido, suifonamido, sulfamyl, acyloxyi, carbalkoxyl, carbamido, nitrile, aldehydo, heterocyclic, di-. alkylamino, acylimino, etc. Specific. compounds is cm=o coming within the above formulas include among others 1,2-propy1ene, furylethylene, isobutylene, vinyl formate, vinyl acetate vinyl propionate, vinyl butyrate, vinyl stearate, vinyl thioacetate, vinyl benzoate, vinyl oxalate, isopropenyl acetate, methylene dimethyl malonate, divinyl formal, acrolein, e-methacrolein, vinyl chloride, vinyl bromide, isopropenyl chloride, vinylidene chloride, vinyl chloroacetate, vinyl tric'hloroacetate, vinyl isocyanate, isopropenyl isocyanate, vinyl acetylene, vinyl urethane, vinyl methyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, vinyl cyclohexyl ketone, vinyl furyl ketone, vinyl p-tolyl ketone, isopropenyl methyl ketone, vinyl methyl ether, vinyl butyi ether, divinyl ether; vinyl phenyl ether, isopropenyl methyl ether, vinyl sulfonamide, vinyl sulphonic acid, vinyl ptolyl sulphoxide, vinyl fl-naphthyl sulphone, vinyl p-tolyl sulphone, isopropenyl methyl sulphone, butadiene, isoprene, chloroprene, 2- acetoxy butadiene-1,3, N-vlnyl acetamide, N-

-viny1 methylacetamide, N-vinyl phenylacetamide, N-vinyl ethylacetamide, N-vinyl methylformamide, N-vinyl acetanilide, N-vinyl p-tolyl acetamide. N-vinyl cyclohexylacetamide, N- vinyl N-methyl butyramide, N-vinyl pyrrole, N-vinyl pyrrolidene, N-vinyl carbazole, vinyl pyridine, vinyl quinoline, styrene, a-methyl styrene, a-chlorostyrene, vinyl phenol, vinyl naphthalene, divinyl benzene, isopropenyl benzene, N-vinyl succinimide, N-vinyl tetrahydrophthalimide, N-vinyl phthalimide, N-vinyl glutarimide, N-vinyl diglycolylimide, N-isopropenyl phthalimide, acrylonitrile, methacrylonitrile, amethoxyacrylonitrile, a-acetozwacrylonitrile, a-

' chloroacrylonitrile, a phthalimidoacrylonitrile,

a-phenoxyacrylonitrile, acrylic acid, metha-, crylic acid, a-ChIOI'OaCIYHC acid, methyl acrylate, methyl methacrylate, methyl ethacrylate, benzyl acrylate, allyl methacrylate, fi-ethoxyethyl acrylate, acrylamide, N-diacetyl acrylamide, N-ethyl acrylamide, N-diethyl acrylamide, etc. Still other unsaturated organic compounds which can .be copolymerized with the new 'diester amides of the invention to give valuable resinous products include the esters, amides and nitriles of maleic, fumaric, maleamic, fumaramic, citraconic and itaconic acids. Examples of the latter compounds include methyl maleate, methyl fumarate, dimethyl maleate, dimethyl fumarate, diethyl fumarate, diisopropyl maleate, dilsopropyl fumarate, maleamide, fumaride, itaconamide, maieonitriie, fumaron'i- The following new diester-amides, polymers thereof, and the rocess of their preparation.

Example 1.N-(fl-methacryloxuethul)' a-methacrillozy propionamide 310 gms. of methacrylic anhydride, 130 gms. of N-(p-hydroxyethyl) lactamide and a small quantity of copper acetate (as an inhibitor of polythe surface.

merization) were mixed together and heated on a steam bath for a period of 18 hours. There were then added 300 c. c. of benzene and the resulting solution washed with a 5 per cent aqueous sodium carbonate solution, and then with water. The benzene layer was dried over anhydrous magnesium sulfate and decolorize d with activated charcoal. The benzene was removed by a stream of warm air blown over A residue of a crystalline material was obtained which, after recrystallization from ether, had a melting point of 85 C. Analysis of the crystals gave a nitrogen content of 5.24 per cent by weight as compared with calculated theory for nitrogen of 5.20 per cent by weight.

The intermediate compound, N-(d-hydroxylethyl) lactamide, employed in the above example was prepared by heating together equimolar quantities of ethyl lactate and ethanolamine in benzene, in a flask fitted to a fractionating column having a variable take-off head. The benzene solution was refluxed for a few minutes, after which time the benzene-ethanol azeotrope was slowly distilled from the mixture. When the theoretical amount of alcohol had been eliminated, the distillate temperature rose to 80 C.,'at which point distillation was continued at 10-15 mm, pressure to remove the benzene as completely as possible. The residue was then distilled at a pressure of 10-15 microns. The distillate obtained was a clear, colorless, viscous liquid. Analysis of this product indicated that a substantially pure product of N-'(fi-hydroxyethyl) lac tamide had been obtained.

Example za N-(p acryloxyethul) a acryloxu propionamide anhydrous calcium sulfate and 5 c. c. of anhydrous pyridine were stirred together for one hour in 800 c. c. of anhydrous dioxane. The reaction mixture was cooled in an ice bath, 270 gms. of acrylyl chloride added and the temperature allowed to rise to room temperature. The mixture was stirred for a period of 17 hours at this temperature, after which time c. c. of pyridine was added and stirring continued for another hour. The mixture was then filtered and the filtrate decolorized with activated charcoal and then concentrated under vacuum to a syrup on a steam bath. The syrup was dissolved in chloroform and the resulting solution washed with dilute sulfuric acid and then with water. The treated chloroform solution was dried over anhydrous calcium sulfate, the chloroform removed at room temperature under vacuum, and the residue of N-(fi-acryloxyethyl) a-acryloxy proexamples illustrate further our a manac I Example 3.Poly-N-(;3 bceyloruethyl) c-llcrzlloxy propionamide 10 gms. of the syrupy monomer prepared in Example 2 were mixed with 50 c. c. of anhydrous dioxane, 0.1 gm. of benzoyl peroxide added and the mixture heated on a steam bath. Within 5 minutes the solution had become cloudy and the polymer started separating out gradually. The mixture was heated for an additional two hours. Methanol was then added and the mixture stirred and filtered. The white, granular polymer so obtained was washed with methanol and dried. It was insoluble in all common organic solvents. The analysis of the polymer gave a nitrogen content of 5.5 per cent by weight indicating thereby that the polymer was made from a substantially pure compound of N-(fi-acryloxyethyl) a-ac'ryloxy propionamide.

, 25 Example 4.-Poly-N-(fi-methacrz/loxyethyl) amethac'ryloacy propionamide Example 5.-C'opolymer of N-(fi-acrylorz ethyl) e-acrylowy propionamide and vinyl acetate 1 gm. of N-(p-acryloxyethyl) c-acryloxy propi-' onamide, gms. of vinyl acetate and 0.05 gm. of benzoyl peroxide were heated together in a sealed tube at 50 C. After 24 hours, a tough, soit mixed together and heated in a clear glass tube in a 60 (2. water bath. A clear, hard, bubbly polymer was obtained. I

Example 9.-Copol;}mer of N-(p-methacrylow /ethyl) a-methacmlomy propionamide and styrene 10 gm. of styrene, 1 gm. of N-fl-methacryloxyethyl) a-methacryloxy propionamide and 0.10 gm. of benzoyl peroxide were mixed together andheated in a clear glass tube in a 60 C. water bath. There was obtained a clear, hard polymer.

Other examples of our new copolymeric compounds, prepared in manner generally similar to the processes described'in the preceding examples are illustrated in the following table:

polymer had formed which was insoluble in all common organic solvents.

Example 6.Copolymer of iV-(p-a-cryloryethyl) e-acrg loxy propionamide and methyl acrylate methyl acrylate and 0.10 gm. of benzoyl peroxide was heated in a sealed tube at 50 C. for a period of 24 hours. A clear, hard and easily millable polymer was obtained. The polymer was insoluble in all common organic solvents. 4

Example 7.C'opolymer of N-(fi-acryloxethzll) a-acryloxy propionamide and styrene A mixture of 2 gms. of N-(p-acryloxyethyl) a-acryloxy propionamide, 18 gms. of styrene and 0.10 gm. of benzoyl peroxide was heated in a sealed tube at 50 C. for a period of 2a hours. There was obtained a clear, hard, easily millable polymer, which was insoluble in all organic solvents.

Example 8.C'opolymer of N-(p-Methacrylorg/ethyl) a-TflthdCTfllOJIZ! propioncmide and methyl methacrylatc 19 gms. of methyl methacrylate, 1 gm. of N- (fi-methacryloxyethyl) a-methacryloxy propionamide and 0.10 gm. of benzoyl peroxide were N-(fl-Methacryloxyethyi) a-methacryioxy Second Monomer, per Characteristics of 20 propionamide, cent by weight I Oopoiymcr per cent by weight 1.. BQMethylmethacryiuto. Hard, clear bubbly and insoluble in organic solvents. 2 08 MethyiMethncrylotc. Do. 5 95 McthyiMethocryintc Do.

1 QQVlnyi acetate Hazy, soft and insolubie in organic solvents. 2 98Vinyiscetate Do. 5 05 Vinyl acetate Do.

i 99 Styrene Hard, clear and insolubic in organic solvcnts. 2 98 Styrene Do. 5 95 Styrene Do.

1 90Diethyliumaratc. Hard, clear and insolubie in organic solvcnts.

2 98 Diethyliumarate.... Do. 6 95 Diothyiiumarate Dc.

1 86.5Iso r0 enylacetatc, Hard, clear and insol- 62.6 let yi fumaratc. uhlc in organic solvcnts.

2 36 Ieo ropenyi acetate, Do.

62D othyllumaratc. 5 35 Isopro enyl acetate, White, hard and insol- Diet yi iumaratc. nbie in organic solvcnts.

' 110' end groups of the diester-amide molecule,

the cross-links between the resin chains are longer and allow more movement between the polymer molecules so cross-linked. As a consequence, the new polymers are less compact and dense, have improved physical properties and are more easily workable by mechanical means, than polymers not containing the above-mentioned connecting group. This permits of wider application of these polymers. For example, any of the new monomeric diester-amides, alone or admixed with one or more other monomeric unsaturated compounds such as those previously mentioned can be employed in solution in an organic solvent or in suspension in a carrier medium such as water, and containing other to materials such as polymerization catalyst, and

if desired, also containing softening and filling materials, to impregnate or coat paper, textile materials such as threads, fibers, fabrics of cellulose, cellulose esters and synthetic textile materials, etc., followed by heating the treated material to polymerize the unsaturated constituents in situ.'

The new diester-amides, alone or admixed with othermonomeric unsaturated compounds such as mentioned previously, may also be polymerized in a mold to a shaped object which subsequently can be worked to final shape by mechanical means such assanding, milling, boring, sawing, etc.

We claim: 1. A compound having formula:

the general structural 5. A polymer of a compound having the general structural formula:

wherein R and R1 each represents a member selected from the group consisting of an atom of hydrogen, a halogen atom, a cyano group, an alkyl group, an aryl group, an aralkyl group; alkoxy group, an aryloxy group,- a cycloalkyl' group. a carboxylic' acid acyl group. a carboxylic acid acyloxy group, a piperidyl group, a carboxyl group. a carbalkoxy group and an amino group.

6. A copolymer of from 0.2 to 99.8 parts by weight of N-(p-acryioxyethyl) a-acryloxy propionamide and from 99.8 to 0.2 parts by weight 01 styrene.

DELBERT D. REYNOLDS. JOHN H. VAN CAMPEN.

REFERENCES CITED The following references are of record in the tile of this patent:

$5 I UNITED STATES PATENTS Number Name Date 2,141,546 Strain Dec. 2'1, 1938 2,311,548 Jacobson et al. Feb. 16, 1943 2,357,283 Peters Sept. 5, 1944 

